Computational and Theoretical Chemistry最新文献

Density functional study on the oxygen evolution reaction mechanism of transition metal doped bimetallic NiCu phosphate surface 过渡金属掺杂双金属NiCu磷酸盐表面析氧反应机理的密度泛函研究

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2025-05-28 DOI: 10.1016/j.comptc.2025.115304

Hamdi Ikhwan , Dzaki Ahmad Syaifullah , Muhammad Arkan Nuruzzahran , Nadhratun Naiim Mobarak , Sasfan Arman Wella , Fadjar Fathurrahman , Ni Luh Wulan Septiani , Adhitya Gandaryus Saputro

{"title":"Density functional study on the oxygen evolution reaction mechanism of transition metal doped bimetallic NiCu phosphate surface","authors":"Hamdi Ikhwan , Dzaki Ahmad Syaifullah , Muhammad Arkan Nuruzzahran , Nadhratun Naiim Mobarak , Sasfan Arman Wella , Fadjar Fathurrahman , Ni Luh Wulan Septiani , Adhitya Gandaryus Saputro","doi":"10.1016/j.comptc.2025.115304","DOIUrl":"10.1016/j.comptc.2025.115304","url":null,"abstract":"<div><div>We have explored the oxygen evolution reaction (OER) activity of both undoped nickel copper phosphate (NiCuPO) and transition metal-doped NiCuPO-M (M = Mn, Fe, Co) surfaces using periodic density functional theory (DFT)-based calculations. Our findings highlight that while the undoped NiCuPO surface exhibits a high overpotential of 0.98 V, the introduction of transition metal doping remarkably enhances the OER performance, reducing the overpotential to as low as 0.41 V in the Mn-doped case, outperforming the widely used IrO<sub>2</sub> catalyst. This enhancement is primarily due to a favorable shift in the <em>d</em>-band center, which increases O* adsorption strength and decreases the OER overpotential. Among the doped systems, Mn and Fe doping demonstrate the most substantial reductions in overpotential, underscoring their potential as efficient catalysts for OER applications.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1250 ","pages":"Article 115304"},"PeriodicalIF":3.0,"publicationDate":"2025-05-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144178422","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Gallium doped AlP monolayers: A promising architecture for gas sensing 掺镓AlP单层：一种有前途的气体传感结构

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2025-05-27 DOI: 10.1016/j.comptc.2025.115301

Naseer H. Kadhim , Tanveer Hussain , Heider A. Abdulhussein

{"title":"Gallium doped AlP monolayers: A promising architecture for gas sensing","authors":"Naseer H. Kadhim , Tanveer Hussain , Heider A. Abdulhussein","doi":"10.1016/j.comptc.2025.115301","DOIUrl":"10.1016/j.comptc.2025.115301","url":null,"abstract":"<div><div>Harmful gases like CO<sub>2</sub>, SO, CO, SO<sub>2</sub>, and H<sub>2</sub>S can lead to serious environmental issues, making the development of effective sensors for their detection essential. This study used density functional theory (DFT)-based first-principles calculations to explore the structural, electronic, optical, and gas-sensing properties of a Ga-doped AlP monolayer towards the selected common pollutants, such as CO<sub>2</sub>, SO, CO, SO<sub>2</sub>, and H<sub>2</sub>S. Van der Waals corrected simulations were employed to find the most effective and sensitive sites for gas adsorption. The results revealed that SO adsorption on a Ga-doped AlP monolayer exhibited a chemical nature, unlike the physical nature observed for the other gases based on the adsorption energy values which were −0.319, −0.712, −0.110, −0.990, and -0.332 for CO₂, SO₂, CO, SO, and H₂S gases respectively. Electron localization function (ELF) analysis of CO<sub>2</sub>, SO<sub>2</sub>, CO, and H<sub>2</sub>S on a Ga-doped AlP monolayer showed delocalized electrons in the interlayer region, indicating that there was no chemical bonding between these gas molecules and the Ga-doped AlP monolayer. Moreover, the adsorption processes were found to affect the optical properties of a Ga-doped AlP monolayer. Overall, the results highlight the promising potential of a Ga-doped AlP monolayer as a gas sensor for the studied gases.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1250 ","pages":"Article 115301"},"PeriodicalIF":3.0,"publicationDate":"2025-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144167776","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Nitrogen doping in carbon nanotube with different mechanical defect shapes as a substrate for aluminum-silver nanoparticle for hydrogen storage technology 在不同机械缺陷形状的碳纳米管中掺杂氮作为贮氢技术中铝银纳米颗粒的衬底

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2025-05-27 DOI: 10.1016/j.comptc.2025.115303

Farid Taherkhani

{"title":"Nitrogen doping in carbon nanotube with different mechanical defect shapes as a substrate for aluminum-silver nanoparticle for hydrogen storage technology","authors":"Farid Taherkhani","doi":"10.1016/j.comptc.2025.115303","DOIUrl":"10.1016/j.comptc.2025.115303","url":null,"abstract":"<div><div>Hydrogen storage has been investigated by using aluminum‑silver nanoalloy supported nitrogen-doped carbon nanotubes (AlAg@NSWC) with various mechanical defect shapes. Current research shows that nitrogen doped in carbon nanotube with different mechanical shapes is a novel substrate device for hydrogen storage on Al–Ag bimetallic nanoparticle surface in AlAg@NSWC. Novelty of such substrate device is significant for hydrogen storage at room temperature on the big size of aluminum nanoparticle especially for line mechanical defect shapes in nitrogen doped carbon nanotube. Another novelty of such material device AlAg@NSWC is ability for hydrogen storage based on standard criteria defined by the United States Department of Energy which is one big achievement. The results indicate that an irreversible structure is observed in (AlAg@NSWC) across all mechanical defect shapes with carbon nanotube structure. There is complicated trend for hydrogen storage versus aluminum doping parameter in silver nanoparticle which is supported by nitrogen-doped in carbon nanotubes with varying mechanical defect shapes at room temperature. There is monotonic trend for hydrogen storage versus pressure of hydrogen on silver nanoparticle surface which is supported on nitrogen-doped carbon nanotubes with different mechanical shapes defect. Additionally, simulation results regarding hydrogen adsorption on metal surfaces as a function of hydrogen pressure align well with available experimental data.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1250 ","pages":"Article 115303"},"PeriodicalIF":3.0,"publicationDate":"2025-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144167777","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Unravelling pyridine substitution position and solvent polarity regulate TICT and ESIPT mechanism for 2-(2-hydroxyphenyl)-benzothiazole derivatives 吡啶取代位置和溶剂极性的解开调节了2-（2-羟基苯基）-苯并噻唑衍生物的TICT和ESIPT机制

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2025-05-26 DOI: 10.1016/j.comptc.2025.115300

You Li , Yilong Wang , Dongxiang Li , Feng Wang , Chaofan Sun

{"title":"Unravelling pyridine substitution position and solvent polarity regulate TICT and ESIPT mechanism for 2-(2-hydroxyphenyl)-benzothiazole derivatives","authors":"You Li , Yilong Wang , Dongxiang Li , Feng Wang , Chaofan Sun","doi":"10.1016/j.comptc.2025.115300","DOIUrl":"10.1016/j.comptc.2025.115300","url":null,"abstract":"<div><div>Substituent group position and solvent polarity have significant effect on optical properties for molecule, which affect practical application value of molecule. In this work, the influence of pyridine group position and solvent polarity on twisted intramolecular charge transfer (TICT) and excited state intramolecular proton transfer (ESIPT) process within 2-(2-hydroxyphenyl)-benzothiazole (HBT) derivatives (oHBT, mHBT and pHBT) had been investigated by theoretical computational methods. The study was carried out using density-functional theory and time-dependent density-functional theory methods. Structural parameters, electron distribution analysis, absorption and fluorescence spectra, non-covalent interaction, infrared spectra and potential energy curves showed that oHBT molecule simultaneously occurs TICT and ESIPT with energy barrierless. Moreover, oHBT and pHBT gradually undergo TICT and ESIPT process. pHBT was more prone to ESIPT process compare with mHBT. ESIPT process of mHBT and pHBT is prone to occur as solvent polarity decreases. This study will broaden the application of luminescent molecules in photophysics field.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1250 ","pages":"Article 115300"},"PeriodicalIF":3.0,"publicationDate":"2025-05-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144139479","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Investigation on halogen atom doping in GaS monolayer and shear strain modulation based on first-principles calculations 基于第一性原理计算的气体单层中卤素原子掺杂及剪切应变调制研究

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2025-05-26 DOI: 10.1016/j.comptc.2025.115299

Xiaotong Yang , Guili Liu , Guoying Zhang

引用次数: 0

Yet another series of correlations based on harmonic oscillator model of aromaticity (HOMA). 基于芳香性谐振子模型（HOMA）的另一系列相关性。

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2025-05-25 DOI: 10.1016/j.comptc.2025.115290

Alice Mischie, Maria Cristina Buta, Bogdan Frecuş, Ana Maria Toader, Fanica Cimpoesu

{"title":"Yet another series of correlations based on harmonic oscillator model of aromaticity (HOMA).","authors":"Alice Mischie, Maria Cristina Buta, Bogdan Frecuş, Ana Maria Toader, Fanica Cimpoesu","doi":"10.1016/j.comptc.2025.115290","DOIUrl":"10.1016/j.comptc.2025.115290","url":null,"abstract":"<div><div>In this work, we check the correlation between computed molecular energies and harmonic oscillator model of aromaticity (HOMA) indices, selecting representative series of isomeric polyaromatic hydrocarbons (PAHs) and derivatives. We designed numeric experiments, enforcing, by constrained geometry optimization equal bond lengths, fixed like in the aromatic reference (benzene), along the conjugated perimeter, checking correlation with HOMA. We refined the HOMA parameterization with substituent-dependent increments, based on the observation C<sub>6</sub>X<sub>3</sub>H<sub>3</sub> and C<sub>6</sub>X<sub>6</sub> substituted benzenes show equal bond lengths around the cycle, appearing then aromatic. The high HOMA indices in the full set of substituted benzenes show a facet of aromaticity as relative resistance to substituent effects, a point confirmed from Valence Bond calculations. The HOMA model can be improved by fine-tuned substituent terms, but this does not lead to improved correlation with energy, showing that the scheme reached its limits of interpretation.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1250 ","pages":"Article 115290"},"PeriodicalIF":3.0,"publicationDate":"2025-05-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144147971","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Interpretation of the correlation energy of atoms, and its dependence with atomic number Z up to Z = 18 解释原子的相关能，以及它与原子序数Z直到Z = 18的关系

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2025-05-23 DOI: 10.1016/j.comptc.2025.115298

Julio A. Alonso , Nicolás A. Cordero

{"title":"Interpretation of the correlation energy of atoms, and its dependence with atomic number Z up to Z = 18","authors":"Julio A. Alonso , Nicolás A. Cordero","doi":"10.1016/j.comptc.2025.115298","DOIUrl":"10.1016/j.comptc.2025.115298","url":null,"abstract":"<div><div>Accurate correlation energies <em>E</em><sub>corr</sub> of neutral atoms with atomic number <em>Z</em> = 1–18, calculated from a combination of experimental and theoretical information, are available in the literature. Those empirical correlation energies show a grossly linear behaviour with <em>Z</em>. However, in more detail <em>E</em><sub>corr</sub> deviates from global linearity and reveals a piece-wise linear behaviour with different slopes as the different electronic shells are progressively filled. This behaviour can be explained by writing <em>E</em><sub>corr</sub> as a sum of pairing-correlation contributions. The pairing-correlation energies have been obtained from the empirical total correlation energies of atoms. Those pairing-correlations are very weak for electrons in different main shells (K, L, M shells) and larger for electrons in the same main shell. In addition, the pairing-correlation energies depend on the angular momenta of the two electronic orbitals. Those features are due to the role of the quantum overlap between the wave functions of the electrons involved in the pairing. Pairs of electrons showing a very small orbital overlap lead to negligible pairing-correlation energies. Keeping a reasonable number of terms, the shell- and angular momentum-dependent pairing-correlation energies explain well the intricate piece-wise linear behaviour of <em>E</em><sub>corr</sub>(<em>Z</em>) up to <em>Z</em> = 18. Also, certain approximations applied to the pairing-correlation energies permit to justify the grossly linear trend of <em>E</em><sub>corr</sub> with <em>Z</em>, and the more precise faster-than-linear behaviour of <em>E</em><sub>corr</sub>(<em>Z</em>).</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1250 ","pages":"Article 115298"},"PeriodicalIF":3.0,"publicationDate":"2025-05-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144139477","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Tuning NO2 selectivity in MoSe2 sensors via metal modification: Fermi-level electronic state control 通过金属修饰调整MoSe2传感器中的NO2选择性：费米能级电子状态控制

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2025-05-22 DOI: 10.1016/j.comptc.2025.115296

Chaohe Song , Lin Tao , Jie Dang , Davoud Dastan , Wensen Wang , Xueyuan Zhang , Lixiang Li , Baigang An

{"title":"Tuning NO2 selectivity in MoSe2 sensors via metal modification: Fermi-level electronic state control","authors":"Chaohe Song , Lin Tao , Jie Dang , Davoud Dastan , Wensen Wang , Xueyuan Zhang , Lixiang Li , Baigang An","doi":"10.1016/j.comptc.2025.115296","DOIUrl":"10.1016/j.comptc.2025.115296","url":null,"abstract":"<div><div>In this study, density functional theory was employed to investigate the selective adsorption of NO<sub>2</sub> on the monolayers of MoSe<sub>2</sub> modified by Ag and Pd. The results of the cohesive energy calculations indicate that the MoSe<sub>2</sub> (4.38 eV) and TM-MoSe<sub>2</sub> (4.35 eV) monolayer materials possess structural stability. The adsorption energy results demonstrate that the metal-doped/loaded structures of Ag-MoSe<sub>2</sub> (−3.91 eV, −4.05 eV) and Pd-MoSe<sub>2</sub> (−3.84 eV, −4.09 eV) exhibit excellent adsorption performance for NO<sub>2</sub>. By means of the d-band center theory, the energy differences caused by Ag/Pd-MoSe<sub>2</sub> during the adsorption process were revealed. Crucially, according to the DOS analysis, when multiple gases coexist, the doped and loaded metals only produce a significant electrical response to NO<sub>2</sub>, effectively eliminating the interference from H<sub>2</sub>O and other gases. In terms of practicality, calculations of the Gibbs free energy and the Einstein diffusion equation show that the doped/loaded Ag/Pd-MoSe<sub>2</sub> monolayers possess thermal stability (< 900 K) and a lower diffusion energy barrier (2.4 kJ mol<sup>−1</sup>). The results indicate that the material with metal doping exhibits a higher response performance to NO<sub>2</sub> than that with metal loading, providing new ideas for the development of novel two-dimensional material-based gas sensors.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1250 ","pages":"Article 115296"},"PeriodicalIF":3.0,"publicationDate":"2025-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144115105","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Structural and electronic properties of neutral and anionic magnesium clusters doped with a carbon atom 掺杂碳原子的中性和阴离子镁簇的结构和电子特性

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2025-05-21 DOI: 10.1016/j.comptc.2025.115294

Zhi Zhao , Jie Zhou , Na Wang , Mingyang Gao , Yu Xie , Xiangjun Kuang , Tingting Song

{"title":"Structural and electronic properties of neutral and anionic magnesium clusters doped with a carbon atom","authors":"Zhi Zhao , Jie Zhou , Na Wang , Mingyang Gao , Yu Xie , Xiangjun Kuang , Tingting Song","doi":"10.1016/j.comptc.2025.115294","DOIUrl":"10.1016/j.comptc.2025.115294","url":null,"abstract":"<div><div>To elucidate the effect of carbon doping in magnesium cluster systems, we employ density functional theory (DFT) calculations to systematically investigate the structural evolution and electronic properties of Mg<sub>n</sub>C<sup>0/−</sup> clusters (<em>n</em> = 2–15). The findings demonstrate that the most stable structure of Mg<sub>n</sub>C<sup>0/−</sup> clusters is three-dimensional at <em>n</em> ≥ 3. Notably, the majority of the lowest-energy Mg<sub>n</sub>C<sup>0/−</sup> configurations (<em>n</em> = 2–15) are not structurally consistent with those derived from substituting a single Mg atom in Mg<sub>n+1</sub> clusters with carbon—a result that shows C doping induces structural reorganization rather than simple substitution. A comparison of the shortest Mg<img>Mg bond lengths reveals that anion incorporation promotes more stable configurations in clusters with <em>n</em> > 7. The reduced HOMO-LUMO gap observed in Mg<sub>n</sub>C<sup>−</sup> clusters (with <em>n</em> > 4) compared to neutral Mg<sub>n</sub>C clusters suggests that anion incorporation enhances their chemical reactivity and metallic character. For all Mg<sub>n</sub>C<sup>0/−</sup> clusters, charge is transferred from the Mg<sub>n</sub> motif to the C atom. A stability analysis reveals that the C<sub>2v</sub>-symmetric Mg<sub>8</sub>C cluster exhibits robust stability. Further investigation into molecular orbitals and bonding of Mg<sub>8</sub>C demonstrates that Mg<sub>8</sub>C not only fulfills 1S<sup>2</sup>1P<sup>6</sup>1D<sup>4</sup>2S<sup>2</sup>1D<sup>6</sup> closed-shell layer structure with 20 valence electrons but also develops strong covalent C<img>Mg and Mg<img>Mg bonds.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1250 ","pages":"Article 115294"},"PeriodicalIF":3.0,"publicationDate":"2025-05-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144139478","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Studies on the bent thoracene with low coordinated bridging units using density functional theory 基于密度泛函理论的低协调桥单位弯曲胸的研究

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2025-05-21 DOI: 10.1016/j.comptc.2025.115295

Sarita Yadav, Pooja, Ravinder Pawar

{"title":"Studies on the bent thoracene with low coordinated bridging units using density functional theory","authors":"Sarita Yadav, Pooja, Ravinder Pawar","doi":"10.1016/j.comptc.2025.115295","DOIUrl":"10.1016/j.comptc.2025.115295","url":null,"abstract":"<div><div>Metallocenophanes are well established as the most prominent organometallic analogs of cyclophanes. In contrast, the intriguing domain of actinocenophanes remains largely unexplored. Hence, density functional theory (DFT) calculations are employed in the present study to investigate a series of [3]thoracenophanes incorporating X-Y-X ansa moieties. These moieties feature a low-coordinated center Y (comprising C, Si, or Ge), stabilized by adjacent donor units X (NMe, O, or S). These ansa-bridged [3]thoracenophanes predominantly feature cyclooctatetraene dianion (COT<sup>2−</sup>) in an eclipsed configuration. Notably, a tilting of the COT<sup>2−</sup>rings is observed when thoracene is bridged with second-row elements, in contrast to the third-row elements. Analysis of the singlet-triplet gap (<span><math><mo>∆</mo><msub><mi>E</mi><mrow><mi>s</mi><mo>−</mo><mi>t</mi></mrow></msub></math></span>) reveals that the triplet states of all investigated carbenes possess higher energy than the corresponding singlet states. Frontier molecular orbital (FMO) analysis further demonstrates that the identity of the heteroatom (X) in the ansa moiety plays a crucial role in stabilizing the low-coordinated carbon (C) of the thoracenophane complex. Furthermore, natural bond orbital (NBO) analysis was conducted to comprehend the stabilization of the resulting carbene-based thoracenophane complexes. The results reveal that, intriguingly, no direct orbital interaction occurs between the thorium center and the ansa bridge, highlighting the primary role of the carbene-based low-coordinated ansa unit in altering the properties through geometrical modifications. This study opens a new avenue for exploring the reactivity patterns of these [3]thoracenophanes toward small-molecule activation and for extending the ansa-bridge design to other actinides for advanced catalytic applications.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1250 ","pages":"Article 115295"},"PeriodicalIF":3.0,"publicationDate":"2025-05-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144134512","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0